Slurrying aluminum chloride for hydrocarbon conversion processes



Sept. 3, 1946.A w. E. KRUsE ETAI.

SLURRYING ALUMINUM CHLORIDE OR HYDROCARBON CONVERSION PROCESSES Filed Deo. 15, 1941 whmmw www w MNNHQWN NQ RSN. Nl NSN uw .w

Patented Sept. 3, 1946 SLURRYING ALUMNUM CHLORIDE FOR. HY-

DROCARBON CONVERSION PROCESSES Willard E. Kruse, Chicago, Ill., Cecil W. Nysewander, `Highland, Ind., and John A. Bolt, Chicago, Ill., assignors to Standard Oil Company, Chicago, Ill., a corporation of Indiana Application December 15, 1941, Serial No. 422,981

2 Claims,

This invention relates to improvements in aluminum chloride hydrocarbon conversion processes and it pertains more particularly to improved methods and means for introducing make-up aluminum chloride into a continuous conversion reactor.

In certain continuous aluminum chloride hydrocarbon conversion processes such as cracking, polymerization, alkylation, isomerization, etc., it is essential to effect a continuous or intermittent introduction of make-up aluminum chloride in order to maintain catalyst activity at the dem sired level. An object of our invention is to provide an improved method and means for supplying make-up aluminum chloride to such a continuous reaction chamber. A further object i to provide a new and improved aluminum chloride isomerization system wherein liquids produced in the system may serve as a vehicle for introducing make-up aluminum chloride.

Considerable trouble has been experienced with the maintenance of aluminum chloride slurries in hydrocarbon charging stocks such, for eX- ample, as light naphtha. Thus in a system for injecting aluminum chloride into a light naphtha isomerization reactor Where a slurry of 2 pounds of finely ground aluminum chloride per gallon of 153 F. end point naphtha feed stock is v employed, at least 75% of the aluminum chloride settles out of the naphtha at a rate of 20 to 30 feet per minute. Furthermore, on contacting the fresh feed the aluminum chloride almost immediately becomes sticky and tends to form a paste. It appears that the naphtha contains a small amount of material which reacts readily with the aluminum chloride to form an adhesive. A thorough drying of the charging stock does not avoid the tendency of the catalyst to agglomerate and become sticky, and it, therefore, appears that the trouble is caused by the nature of the charging stock itself or by a trace of ad hesive-forming materials in said charging stock. An object of our invention is to avoid the formation of sticky or adhesivesubstances in suchcatalyst slurries and to avoid the clogging of line-s, pumps, valves, injection means, etc., through which the slurry must be passed en route to the reaction chamber.

A further object of our invention is to vprovide a more efcient utilization of liquids separated from isomerization products in an isomerization reaction system. Other objects will become ap-4 parent as the .detailed description of ourinvention proceeds.V

We have discovered that if the hydrocarbon (Cl. Zim-683.5)

feed stock such as light naphtha is previously treated with aluminum chloride before it is employed for making up the aluminum chloride slurry, the resulting slurry will remain in suspended form for an extended period of time. Slurries of make-up aluminum chloride which are formed by the use of such pretreated naphtha can be readily handled and injected into the system. Even in the case of a pretreated slurrying vehicle, however, it is desirable to avoid a prolonged time between slurry formation and actual slurry injection.

We have discovered that a remarkably and unusually stable aluminum chloride slurry results from the use as slurrying agents of liquids which have already undergone treatment in the isomerization reaction itself. Products directly from the reactor (or from the settlers following the reactor) are usually contaminated with complex material that would be deleterious in the slurrying step; products from these points also contain dissolved hydrogen chloride which promotes compex formation and which is hence objectionable in the slurrying step. However, the cooled product from which hydrogen chlorideY has been removed is an excellent source of slurrying liquid. Also, the heavy ends of the isomerization products, i. e., components boiling just above neoheXane, are also effective for producing a stable slurry which is substantially free from sticky and adhesive materials; the recycling of this heavy isomate fraction serves the additional and im portant function of increasing the neohexane production in the isomerization system.

It might be supposed that since products from the isomerization system are effective slurrying agents that light iso-parains would likewise be effective. A test with isooctane as a slurrying agent showed that this agent was even worse than untreated light naphtha charging stock. The use of isooctane resulted in an adhesive mass that settled and stuck to the bottom of a container. Isooctane is thus utterly worthless as a slurrying agent.

The sludge produced in the aluminum chloride pretreating step (or spent sludge from the isomerization reaction Zone) may be introduced into av high pressure hydrogen chloride generator and treated ywith a hydrolyzing agent such as sulfuric acid or water in order to supply at least a part of the necessary make-up hydrogen chloride which is required in the isomerization reaction. Alternatively it may be used as catalyst material in the isomerization reactor, being introduced separately or with recycled complex and not with the make-up catalyst slurry.

Our invention will be more clearly understood from the following detailed description read in conjunction with the accompanying drawing which forms a part of this specification and which is a schematic flow diagram of an improved system for isomerizing light naphtha.

While our invention is applicable to a wide variety of aluminum chloride-hydrogen chloride hydrocarbon conversion processes, it is particularly applicable in the process for isomerizing a light naphtha consisting essentially of parainic hydrocarbons of the butane to hexane boiling range. Referring to the drawing, a virgin naphtha charging lstock is introduced by pump iil through heat exchanger II to fractionating tower I2 which is provided with suitable heating means I3 at its base and which is operated under such conditions that heptanes and heavier hydrocarbons are removed from the base through line I4. An intermediate cut consisting essentially of C5, Ce or C5 and Cs hydrocarbons may be withdrawn by pump I5 (a plurality of towers will be used for the fractionation in actual practice, the side stream being a diagrammatic representation) through heater I5 and then split into two streams, the 'small stream passing by line I'I to pretreating tank I3 and the large Istream pas-sing by line I 9 to hydrogen chloride absorber 2B. When the make-up aluminum chloride is slurried with recycled material. the valve in line I 'I may be closed and all of the charging stock may be passed to the absorber.

Overhead from fractionator I2 is withdraw):`

through line 2l and cooler 22 to reflux drum 23 from which' uncondensed gases may be vented through line 24. When an intermediate cut has been withdrawn, the reflux condensate may consist essentially of butane (or a mixture of butanes and pentanes) which is withdrawn from the base of the drum by means of pump 25. A portion of this reflux condensate may be returned through line 26 to serve as reflux in the top of tower I 2. Reux condensate from this source may also be introduced through line 2l to line I7, through line 23 to line I9, through line 29 to a hydrogen absorber system, or through line 30 to storage or to a point of use elsewhere in the refinery.

The hydrogen chloride absorber 2i! is preferably operated under a superatmospheric pressure which may range from about 50 to 350 cr more pounds per square inch but which is preferably in the general vicinity of 200 to 250 pounds rer square inch. Make-up hydrogen chloride may b2 introduced through lines 3| or 33 and a gaseous stream containing hydrogen chloride is introduced at the base of this absorber through line 32. Unabsorbed gases, chiefly hydrogen, methane, ethane, etc., leave the top of the absorber through line 34 and may be vented from the system through line 35 or introduced through line 36 together with additional hydrogen containing gases from line 31 into the base of absorber 33, a suitable compressor 39 being employed for this pur-- pose. Butane from line 29 may be introduced by pump 49 and line 4I to the top of absorber 38. This absorber may be provided with suitab`e baffles or bubble plates and it may be operated at a temperature of about 100 F. and a pressure of about 900 pounds per square inch. Gaseous hydrocarbons are absorbed and introduced through line 42 and pressure reducing valve 43 into separating chamber 44 which may Operate under about 35 pounds pressure. Hydrocarbon gases may be purged from the system through line 45 and the butane from the base of the separator' may be returned through line 45, pump 4i) and line 4I back to the top of the absorber. Hydrogen leaves the top of the absorber through line 4l.

The charging stock-hydrogen chloride solution from the base of absorber 20 is forced by pump 48 4through heater 49 and lines 55 and 50a into isomerization reactor 5I. Hydrogen from line 4l or from outside source 52 is introduced by compressor 53 either into line 50 or directly into reactor 5I. Make-up aluminum chloride n the form of a slurry is introduced into reactor 5I from a slurry tank by means of pump 54 and line 55. Aluminum chloride or complex from other parts of the system are introduced into the reactor through line 56.

The reactor contains a large amount of aluminum chloride catalyst material which is usually in the form of an aluminum chloride hydrocarbon complex. The charging stock passes upwardly through this catalyst material in nely divided dspersed phase at a space velocity of about .2 to 4 volumes of liquid charging stock per hour per Volume of catalyst material. The temperature in the reactor is within the range of 100 to 400 F. and is usually in the general viciniy of 250 F. The pressure in the reactor is in the range of 500 to 1500 pounds per square inch and may be about 850 pounds per square inch. Reaction products are withdrawn from the top of reactor 5I through lines 57 and 58 to warm settler 59 and thence through line EU, cooler 6I and pressure reducing Valve 62 to cool settler 63. Gases leave the top of the cool settler through line 64. and are returned by line 32 to hydrogen chloride absorber 20.

Clear product liquids leave the cool settler through line 65 and are introduced by pump 56 into hydrogen chloride Stripper column 61 which is provided with a suitable heating means 68 at its base. The overhead from this stripper may be passed through line 69 to line -32 for recyclingV or may be passed through cooler I0 to reux drum 'I I. Gases from the top of this drum pass by linesy 12 and line 32 to the hydrogen chloride absorber 20 and liquids from the base of this drum may be either returned by line 'I3 for use as reflux in the top of the stripper or may be withdrawn through line 14. The product from line 74 is chieily isobutane and when it is passed to an aluminum chloride alkvlation system it is unnecessary that dissolved hydrogen chloride be removed therefrom. Stripper tower S'I may thus function both as a hydrogen chloride stripper and as a stabilizer tower.

Liquid products from the base of tower El are passed directly by line 'I5 or through cooler 'I6 to caustic scrubber and Wash tower TI. Caustic may be introduced through line 78 and water through line 79. The wash water may be trapped out above the caustic inlet or the water and caustic may both be removed from the base of the tower through line 80.

The neutralized and water washed product is withdrawn from the top of the wash tower through line BI and it may either be withdrawn Vfrom the system through line 82 or passed through line 83 and heat exchanger 84 to stabilizer or fractionating tower 85 which is provided with a suitable heating means 86 at its base.k

Heavy isomate or hydrocarbon material may be withdrawn from thebase of the stabilizer through line 81 and removed from the system through cooler 92toreflux drumBfrom which gases he vented through line. 8.4... A portion .ofthe vreflux may be returned'hyypump .95 Athrough line 96 to theztop of the .stabilizer and a, lightfraction consisting,V iorexar'npl :chiefly .of butanes maybe .withdrawn from .thefsystem through line Instead of employing a .single'reactor we may employ a multiple reactorV system. Thus .charging stockv with ahsorbedhydrogen chloride :may be introduced throughlineb to reactor Elib and make-up .catalyst `may be .added to .this reactor through :line 5517. Alternatively, the products leaving the top of reactor'l may be passed by line .98..tl1rough cooler 99 .and to reactor 5Ib and the products from the top'of reactor 5|b Amay be passed through line and line v58 to warmsettler 59.

Catalyst from the Vbase of reactor `5|b may lbe withdrawn by pump |.0I and either withdrawn from the system through .line |02, passed by lines |03 and 5B .to reactor 5I or passed. through, lines |03 to line |04 to "hydrogen Vchloride recovery drum |65. Catalystmay.be'withdrawn from the base of reactor. 5| by pump |05 and either with drawn from the system through line |01, passed to reactor EIb .through line `I08'or passed to the hydrogen chloride recovery drum through lines |09 and |114.L `Material from lines ,|02 or |01 or.

recovery drum I05or to one of .the reactors 5I or 5Ib through lines 5,6 or IDB.

The lpretreating with aluminum chloride in lump form, supported form or complex form in chamber I8 alters thewcharaoter of the charging stock in such a Way as to prevent the formation of sticky adhesive compounds with the powdered aluminum chloride in slurry tank IIB. In the absence .of ,the nretreating step the. slurry 'formed .in tank ,|.|8 rapidly plugs lines 55, 55a, etc. and

the pumps, valves, etc. associated therewith. The pretreating step insures'the formation of a slurry which-is. sufiiciently free from sticky .and adhesive materials so that it will not agglomerato and will not cause aplugging of the transfer limes,

' pumps and valves.

Y drogen chloride is returned through ,line |21 and both may be .employed to pretreat naphtha in tank I8.

settieu catalyst material from settler 59 may be passed through lines .III and |08 to reactor chamber 5|b or through lines 2 and 56 to reactor 5|. Precipitated catalyst material from cool settler B3 may be pumped as a slurry by pump ||3 through lines ||4 and 90 to the slurry tank but is preferably pumped through lines I I5 and |08 to reactor 5|b or through lines III;` and 56 to reactor 5|.

Our invention is primarily connected with the supplying of make-up aluminum chloride to the isomerization system hereinabove described. Powdered aluminum chloride from source ||1 is introduced into slurry tank ||8 by means of any suitable hopper, screw feeder, or other feeding means. Slurry tank ||8 may be provided with a suitable mixer or high speed stirrer driven by motor I 20. The oil for making up the slurry may be obtained from pretreating tank I8 through line |2| or from various parts of the system through line 90.

In prereating tank I8 the aluminum chloride is preferably in lump form or is deposited on a suitable support such as Kieselguhr or is in the form of a hydrocarbon complex. Thus lump aluminum chloride may be introduced from source |22 and may be retained in the pretreating chamber by screen support |23. Light naphtha from line enters pretreating chamber IIB below screen |23 and passes upwardly through the bed of lump aluminum chloride, leaving the top of the pretreating chamber through line I2 I. A viscous brownish red complex may be formed by the contacting of charging stock in this pretreating chamber and since this oil complex is heavier than charging stock it settles to the base of the pretreating chamber and may be withdrawn therefrom through line |24 to hydrogen chloride line 32 to absorber Z0. If water is used as a hydrolyzing ragent it should be employed in lless than stoichiometric amounts in order that the recovered hydrogen chloride may be substantially anhydrous. Larger amounts of recovered khydrogen chloride may be obtained by the use of sulfuric acid and such use is particularly advisable where sludge cokermeans `are available Vfor recovering the sulfuric acid.

The hydrogen chloride recovered from chamber |05 mayA notbe suiiicient to supply all of the required make-up `hydrogen chloride andV additional hydrogen chloride may, therefore, have to be added through line .3L The additional `hydrogen chloride may be generated in a high pressure generator |21 luy-adding a hydrogen supplying agent through line |28 and a chlorine` supplying agent through line |29. The by-oroduct vfrom .this generator mayy be withdrawn through line |30 and the produced hydrogen chloride may be introduced directly through line 33 into the base of the absorber 20 without the necessity of employing pumps or purifying means. The hydrogen supplying agent may be hydrogen itself, a gas containing hydrogen (e. g., from line 35), a hydrocarbon or sulfuric acid.` The chlorine supplying agent may be chlorine gas, sodium chloride, hydrochloric acid, etc. Thus chlorine may be introduced through line |29 and burned with an excess of hydrogen or hydrogen containing gas introduced through line |28 or reacted with a hydrocarbon introduced through line |28. Sodium chloride or aqueous hydrochloric acid may be introduced through line |29 and sulfuric acid may be introduced through line |28.

While the pretreating of a portion of the feed stock with aluminum chloride makes it possible to produce a pumpable slurry in tank ||8 we have found that a superior type of slurry is produced by employing liquids recycled from the system through line 8.0. Such liquid may be withdrawn from the product stream between cooler 'I6 and wash tower and passed to tank |20 through lines |3I, 89 and 90. 'I'he product at this point is substantially anhydrous and is free from catalyst material and hydrogen chloride. The "pretreatment of the charging stock for the preparation of a slurry Vehicle is in this instance effected in the isomerization reactor itself.

Another liquid Which produces a highly desirable type of slurry is that obtained from the base of stabilizer or fractionator column B5 from lines 81 and 89. This liquid may consist' chiey of methyl pentanes and unisomerized normal hex;` ane. By using this liquid as a slurrying agent for make-up aluminum chloride we not only obtain a highly satisfactory slurry but We 'also obtain increased yields of neohexane, i. e.; We obtain isomerization products of higher octane number and hence of greater value as aviation fuel blending stocks.

While We have described specific examples of our invention in considerable detail it should be understood thatour invention is not limited to these particular examples nor to the specic conditions'recited therein since other examples and other operating conditions will be apparent to those skilled in the art from the above detailed description. `We claim:

l. The method of isomerizing a paraiinic hydrocarbon charging stock boiling within the butane to hexane boiling range which method comprises absorbing hydrogen chloride in said charging stock in an absorption zone to form a hydrogen chloride solution, heating said solution toY isomerization temperature and introducing the heated solution at a low level in a continuous isomerization zone containing a large amount of liquid aluminum chloride-hydrocarbon complex catalyst material, effecting isomerization of said charging stock in said isomerization Zone, Withdrawing an isomerization product stream containing dissolved catalyst material and hydrogen chloride from the top of the isomerization zone to a settling zone, removing catalyst material from said stream in said settling zone, introducing the stream Whichstill contains hydrogen chloride from said settling zone to a stripping Zone, stripping hydrogen chloride from said stream in said stripping zone', returning hydrogen chloride containing gases from the top of the stripping zone tothe absorption zone, venting unabsorbed gases from the top of the absorption zone, making up an aluminum chloride slurry of iinely divided solid aluminum chloride particles in a portion of the stream after hydrogen chloride has been stripped therefrom and introducing said aluminum chloride slurryV into said isomerization zone for maintaining the activity of the liquid aluminum chloride-hydrocarbon complex material contained therein. Y

2. The method of isomerizing a parainic hydrocarbon charging stock boiling Within the butane to hexane boiling range Which method comprises adding hydrogen chloride to said charging stock, and introducing the charging stock With added hydrogen chloride at a low level into a continuous isomerization zone containing a large amount of liquid aluminum chloride-hydrocarbon complex catalyst material, eecting isomerization of said charging stock in said isomerization zone, withdrawing a product stream containing catalyst material and hydrogen chloride from the upper part of said isomerization zone to a settling Zone, removing catalyst material from said stream in said settling zone, introducing said stream from said settling zone to a stripping zone, stripping hydrogen chloride from said stream in said stripping zone, treating the stripped stream with caustic to effect neutralization thereof, fractionating the neutralized product stream to obtain a plurality of fractions including a'heavy fraction, making up an aluminum chloride slurry of finely divided aluminum chloride particles in a portion of said heavy fraction and introducing said aluminum chloride slurry into said continuous isomerization zone for Amaintaining the activity of the liquid aluminum chloride-hydrocarbon complex catalyst material contained therein.

WILLARD E.V KRUSE. CECIL W. NYSEWANDER. JOHN A. BOLT. 

